A sewage treatment agent containing 1,4-butanediol and preparation method thereof

Abstract

The present invention relates to the technical field of sewage treatment, and discloses a sewage treatment agent containing 1,4-butanediol and a preparation method thereof. The present invention is provided by adding 1,4-butanediol, quaternized sodium phenylsulfonate, silicon-modified phenolic resin and polyacrylamide into a stirrer, stirring, and obtaining the sewage treatment agent containing 1,4-butanediol after completion. The quaternary ammonium salt group in the sewage treatment agent containing 1,4-butanediol of the present invention removes heavy metal ions in sewage by complexation, and the sulfonic acid group can also effectively remove heavy metal ions; the triazine structure in the quaternized sodium phenylsulfonate, the triazine group is a six-membered heterocyclic structure containing three nitrogen atoms, can be used as a coordinating atom to form a stable coordination with metal ions, and effectively removes heavy metal ions; the phenolic resin and the cardanol structure in the silicon-modified phenolic resin have good adsorption effect, effectively remove heavy metal ions, and also contain a large amount of quaternary ammonium salts, which work together to remove heavy metal ions.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment, in particular to a sewage treatment agent containing 1,4-butanediol and a preparation method thereof. Background Art

[0002] At present, environmental protection has become a world concern. The discharge of industrial wastewater will cause certain harm to the environment. Therefore, it is necessary to develop a sewage treatment agent to make the sewage meet the discharge requirements. If it is not controlled, it will flow into the river, causing the river to be seriously polluted, which will further harm the human body. For example, patent CN110563162A discloses a sewage treatment agent, its preparation method and application. The biological active substances of the sewage treatment agent of the invention are highly stable and active, and have good adsorption capacity, flocculation capacity and biodegradability. However, its components are relatively complex and contain polyaluminum chloride, in which the aluminum element will remain in the water, which will cause harm to the human body. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a sewage treatment agent containing 1,4-butanediol and a preparation method thereof, which can effectively remove heavy metal ions in sewage.

[0005] (II) Technical solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: a 1,4-butanediol-containing sewage treatment agent, comprising the following components by weight: 8-15 parts by weight of 1,4-butanediol, 5-9 parts by weight of quaternized sodium phenyl sulfonate, 4-8 parts by weight of silicon-modified phenolic resin, and 6-12 parts by weight of polyacrylamide.

[0007] Preferably, the preparation method of the quaternized sodium phenylsulfonate is:

[0008] (1) In a nitrogen atmosphere, hexamethyldisilazane and propenyl-1,3-sultone are added to a reaction kettle containing acetonitrile solvent, stirred evenly, and chloroplatinic acid catalyst is added thereto, reacted at 65-80° C. for 45-60 minutes, and then cooled to room temperature to obtain tertiary aminosultone;

[0009] (2) adding 8-12 parts by weight of tertiary amino sultone and 3-5 parts by weight of tris(4-aminophenyl)amine to an N,N-dimethylformamide solvent, and then adding a 4-6% by weight sodium hydroxide solution thereto, heating to 70-90° C. for reaction, and after the reaction, removing the solvent by distillation under reduced pressure, washing and drying to obtain sodium sulfonate modified silane;

[0010] (3) adding sodium sulfonate-modified silane and 2-amino-3-chloropropionic acid to N,N-dimethylformamide solvent, reacting at 75-85°C for 10-12 hours, and then rotary distilling, filtering and drying to obtain an intermediate;

[0011] (4) Add 4,6-diamino-2-hydroxy-1,3,5-triazine and the intermediate to dimethyl sulfoxide, stir to dissolve and heat to 130-150°C, then dropwise add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, stir and reflux for 12-16 hours, cool, precipitate, filter and wash after the reaction to obtain quaternized sodium phenylsulfonate.

[0012] Preferably, the mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst in (1) is 1:1.2-1.4:0.02-0.03.

[0013] Preferably, the reaction time in (2) is 8-14 hours.

[0014] Preferably, the mass ratio of sodium sulfonate modified silane to 2-amino-3-chloropropionic acid in (3) is 1:2.1-3.4.

[0015] Preferably, in said (4), the mass ratio of 4,6-diamino-2-hydroxy-1,3,5-triazine, intermediate, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine is 0.4-0.8:1:0.01-0.03:0.02-0.03.

[0016] Preferably, the preparation method of the silicon-modified phenolic resin is:

[0017] S1. Add 7-15 parts by weight of 4-chloromethylphenol and 6-10 parts by weight of sodium sulfonate modified silane to N,N-dimethylformamide solvent, stir to dissolve, react at 65-80 ° C for 5-8h, and then distill under reduced pressure, filter and dry to obtain quaternized phenol;

[0018] S2. Dissolve 12-16 parts by weight of phenol in water, then add 1-2 parts by weight of cardanol, 0.6-1 parts by weight of quaternized phenol, 0.3-0.6 parts by weight of oxalic acid dihydrate and 8-13 parts by weight of polyformaldehyde, heat to 80-90°C and react for 2-4 hours to obtain silicon-modified phenolic resin.

[0019] Preferably, the preparation method of the 1,4-butanediol-containing sewage treatment agent is: 1,4-butanediol, quaternized sodium phenyl sulfonate, silicon-modified phenolic resin, and polyacrylamide are added to a stirrer, and stirred for 20-25 minutes to obtain the 1,4-butanediol-containing sewage treatment agent.

[0020] 3. Beneficial technical effects

[0021] The invention provides a sewage treatment agent containing 1,4-butanediol by adding 1,4-butanediol, quaternized sodium phenyl sulfonate, silicon-modified phenolic resin and polyacrylamide into a stirrer and stirring the mixture.

[0022] The silicon-hydrogen bond in hexamethyldisilazane and the alkenyl in propenyl-1,3-sultone undergo addition reaction to introduce a tertiary amine group, thereby obtaining a tertiary amine sultone. The tertiary amine sultone reacts with tri(4-aminophenyl)amine to generate a sodium sulfonate group, while increasing the degree of substitution of the tertiary amine group, thereby obtaining a sodium sulfonate-modified silane, which then reacts with the chlorine in 2-amino-3-chloropropionic acid to generate a large amount of quaternary ammonium salts, while introducing an amine group and a carboxyl group, thereby obtaining an intermediate, and 4,6- The amino group in diamino-2-hydroxy-1,3,5-triazine reacts with the carboxyl group in the intermediate to generate a large number of amide groups, while increasing the degree of substitution of the quaternary ammonium salt, thereby obtaining quaternized sodium phenylsulfonate; the chlorine in 4-chloromethylphenol reacts with the tertiary amine group in the sodium sulfonate-modified silane to generate a quaternary ammonium salt, while introducing a phenolic hydroxyl group, thereby obtaining quaternized phenol; phenol, cardanol, quaternized phenol, dihydrated oxalic acid, and polyformaldehyde are reacted to obtain a silicon-modified phenolic resin.

[0023] The quaternary ammonium salt group in the sewage treatment agent containing 1,4-butanediol of the present invention removes heavy metal ions in sewage through complexation. The sulfonic acid group contains sulfur atoms with high electron cloud density, which makes it easy to complex with chromium ions and lead ions in wastewater to form tiny flocs and form precipitation through electrical neutralization with the quaternary ammonium salt group, thereby effectively removing heavy metal ions. The triazine group structure in the quaternized sodium phenyl sulfonate is a six-membered heterocyclic structure containing three nitrogen atoms, which can be used as a coordinating atom to form a stable coordination with metal ions, thereby effectively removing heavy metal ions. Moreover, a large number of amide groups are grafted on the triazine group, thereby effectively removing medium and heavy metal ions. The phenolic resin and cardanol structures in the silicon-modified phenolic resin have good adsorption effects, thereby effectively removing heavy metal ions. The sulfonic acid group also contains a large number of quaternary ammonium salts, which work together to remove heavy metal ions. The 1,4-butanediol of the present invention itself can also remove heavy metal ions. DETAILED DESCRIPTION Example 1

[0024] (1) In a nitrogen atmosphere, hexamethyldisilazane and propenyl-1,3-sultone were added to a reaction kettle containing acetonitrile solvent, and the mixture was stirred evenly. A chloroplatinic acid catalyst was added thereto, wherein the mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst was 1:1.2:0.02. The mixture was reacted at 65° C. for 45 minutes, and then cooled to room temperature to obtain a tertiary aminosultone.

[0025] (2) adding 8 parts by weight of tertiary amino sultone and 3 parts by weight of tris(4-aminophenyl)amine to N,N-dimethylformamide solvent, and then adding 4% by weight sodium hydroxide solution thereto, heating to 70° C. and reacting for 8 hours, and after the reaction, removing the solvent by distillation under reduced pressure, washing and drying to obtain sodium sulfonate modified silane;

[0026] (3) adding sodium sulfonate-modified silane and 2-amino-3-chloropropionic acid to N,N-dimethylformamide solvent, wherein the mass ratio of sodium sulfonate-modified silane to 2-amino-3-chloropropionic acid is 1:2.1, reacting at 75° C. for 10 h, and then rotary distilling, filtering and drying to obtain an intermediate;

[0027] (4) Add 4,6-diamino-2-hydroxy-1,3,5-triazine and the intermediate to dimethyl sulfoxide, stir to dissolve and heat to 130°C, then dropwise add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, wherein the mass ratio of 4,6-diamino-2-hydroxy-1,3,5-triazine, the intermediate, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine is 0.4:1:0.01:0.02, stir and reflux for 12 hours, cool, precipitate, filter and wash after the reaction to obtain quaternized sodium phenyl sulfonate;

[0028] (5) Add 7 parts by weight of 4-chloromethylphenol and 6 parts by weight of sodium sulfonate-modified silane to N,N-dimethylformamide solvent, stir to dissolve, react at 65° C. for 5 h, and then distill under reduced pressure, filter and dry to obtain quaternized phenol;

[0029] (6) dissolving 12 parts by weight of phenol in water, then adding 1 part by weight of cardanol, 0.6 parts by weight of quaternized phenol, 0.3 parts by weight of oxalic acid dihydrate and 8 parts by weight of paraformaldehyde, heating to 80° C. and reacting for 2 hours to obtain a silicon-modified phenolic resin;

[0030] (7) Add 8 parts by weight of 1,4-butanediol, 5 parts by weight of quaternized sodium phenyl sulfonate, 4 parts by weight of silicon-modified phenolic resin, and 6 parts by weight of polyacrylamide into a stirrer and stir for 20 minutes to obtain a wastewater treatment agent containing 1,4-butanediol. Example 2

[0031] (1) In a nitrogen atmosphere, hexamethyldisilazane and propenyl-1,3-sultone were added to a reaction kettle containing an acetonitrile solvent, and the mixture was stirred evenly. A chloroplatinic acid catalyst was added thereto, wherein the mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst was 1:1.4:0.03, and the mixture was reacted at 80° C. for 60 min. After the reaction was completed, the mixture was cooled to room temperature to obtain a tertiary aminosultone;

[0032] (2) adding 12 parts by weight of tertiary amino sultone and 5 parts by weight of tris(4-aminophenyl)amine to N,N-dimethylformamide solvent, and then adding 6% by weight sodium hydroxide solution thereto, heating to 90° C. to react for 14 h, and after the reaction, removing the solvent by distillation under reduced pressure, washing and drying to obtain sodium sulfonate modified silane;

[0033] (3) adding sodium sulfonate-modified silane and 2-amino-3-chloropropionic acid to N,N-dimethylformamide solvent, wherein the mass ratio of sodium sulfonate-modified silane to 2-amino-3-chloropropionic acid is 1:3.4, reacting at 85° C. for 12 h, and then rotary distilling, filtering and drying to obtain an intermediate;

[0034] (4) Add 4,6-diamino-2-hydroxy-1,3,5-triazine and the intermediate to dimethyl sulfoxide, stir to dissolve and heat to 150°C, then dropwise add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, wherein the mass ratio of 4,6-diamino-2-hydroxy-1,3,5-triazine, the intermediate, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine is 0.8:1:0.03:0.03, stir and reflux for 16 hours, cool, precipitate, filter and wash after the reaction to obtain quaternized sodium phenyl sulfonate;

[0035] (5) Add 15 parts by weight of 4-chloromethylphenol and 10 parts by weight of sodium sulfonate-modified silane to N,N-dimethylformamide solvent, stir to dissolve, react at 80° C. for 8 h, and then distill under reduced pressure, filter and dry to obtain quaternized phenol;

[0036] (6) dissolving 16 parts by weight of phenol in water, then adding 2 parts by weight of cardanol, 1 part by weight of quaternized phenol, 0.6 parts by weight of oxalic acid dihydrate and 13 parts by weight of paraformaldehyde, heating to 90° C. for reaction for 4 hours, and obtaining a silicon-modified phenolic resin after the reaction;

[0037] (7) Add 15 parts by weight of 1,4-butanediol, 9 parts by weight of quaternized sodium phenyl sulfonate, 8 parts by weight of silicon-modified phenolic resin, and 12 parts by weight of polyacrylamide into a stirrer and stir for 25 minutes to obtain a wastewater treatment agent containing 1,4-butanediol. Example 3

[0038] (1) In a nitrogen atmosphere, hexamethyldisilazane and propenyl-1,3-sultone were added to a reaction kettle containing acetonitrile solvent, and the mixture was stirred evenly. A chloroplatinic acid catalyst was added thereto, wherein the mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst was 1:1.3:0.025. The mixture was reacted at 72° C. for 52.5 min, and then cooled to room temperature to obtain a tertiary aminosultone.

[0039] (2) adding 10 parts by weight of tertiary amino sultone and 4 parts by weight of tris(4-aminophenyl)amine to N,N-dimethylformamide solvent, and then adding 5% by weight sodium hydroxide solution thereto, heating to 80° C. and reacting for 11 hours, and after the reaction, removing the solvent by distillation under reduced pressure, washing and drying to obtain sodium sulfonate modified silane;

[0040] (3) adding sodium sulfonate-modified silane and 2-amino-3-chloropropionic acid to N,N-dimethylformamide solvent, wherein the mass ratio of sodium sulfonate-modified silane to 2-amino-3-chloropropionic acid is 1:2.75, reacting at 80° C. for 11 h, and then rotary distilling, filtering and drying to obtain an intermediate;

[0041] (4) Add 4,6-diamino-2-hydroxy-1,3,5-triazine and the intermediate to dimethyl sulfoxide, stir to dissolve and heat to 140°C, then dropwise add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, wherein the mass ratio of 4,6-diamino-2-hydroxy-1,3,5-triazine, the intermediate, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine is 0.6:1:0.02:0.025, stir and reflux for 14 hours, cool, precipitate, filter and wash after the reaction to obtain quaternized sodium phenylsulfonate;

[0042] (5) Add 11 parts by weight of 4-chloromethylphenol and 8 parts by weight of sodium sulfonate-modified silane to N,N-dimethylformamide solvent, stir to dissolve, react at 72° C. for 6.5 h, and then distill under reduced pressure, filter and dry to obtain quaternized phenol;

[0043] (6) dissolving 14 parts by weight of phenol in water, then adding 1.5 parts by weight of cardanol, 0.8 parts by weight of quaternized phenol, 0.45 parts by weight of oxalic acid dihydrate and 10.5 parts by weight of polyformaldehyde, heating to 85° C. for reaction for 3 hours, and obtaining a silicon-modified phenolic resin after the reaction;

[0044] (7) 11.5 parts by weight of 1,4-butanediol, 7 parts by weight of quaternized sodium phenyl sulfonate, 6 parts by weight of silicon-modified phenolic resin, and 9 parts by weight of polyacrylamide were added into a stirrer and stirred for 22.5 minutes to obtain a wastewater treatment agent containing 1,4-butanediol.

[0045] Comparative Example 1

[0046] This comparative example is compared with Example 3, except that no quaternized sodium phenyl sulfonate is added.

[0047] Comparative Example 2

[0048] The difference between this comparative example and Example 3 is that no silicon-modified phenolic resin is added.

[0049] Take 200mL of wastewater into a beaker. 2+ , and Pb 2+ The initial concentration of the wastewater was 100 mg / L. The wastewater treatment agent was added to the wastewater, and the wastewater was ultrasonically dispersed for 5 minutes and then placed on a shaker for 12 hours. The supernatant was taken and the Cd content in the supernatant was determined by ICP. 2+ and Pb 2+ The concentration after adsorption, the removal rate of heavy metal ions w = (initial concentration-concentration after adsorption) / initial concentration, the test results are shown in Table 1.

[0050] Table 1: Heavy metal ion removal rate test.

[0051] project <![CDATA[Cd 2+ Removal rate (%)]]> <![CDATA[Pb 2+ Removal rate (%)<!-- 4 --> ]]> Example 1 90.2 90.5 Example 2 92.5 92.7 Example 3 90.7 91.3 Comparative Example 1 54.6 52.6 Comparative Example 2 53.1 51.4

[0052] It can be seen from Table 1 that Examples 1-3 of the present invention have better removal effects on heavy metal ions than Comparative Examples 1-2, indicating that they have better removal effects.

[0053] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A sewage treatment agent containing 1,4-butanediol, characterized in that: The invention comprises the following components by weight: 8-15 parts by weight of 1,4-butanediol, 5-9 parts by weight of quaternized sodium phenyl sulfonate, 4-8 parts by weight of silicon-modified phenolic resin, and 6-12 parts by weight of polyacrylamide; The preparation method of the quaternized sodium phenyl sulfonate is: (1) In a nitrogen atmosphere, hexamethyldisilazane and propenyl-1,3-sultone are added to a reaction kettle containing acetonitrile solvent, stirred evenly, and chloroplatinic acid catalyst is added thereto, reacted at 65-80° C. for 45-60 minutes, and then cooled to room temperature to obtain tertiary aminosultone; (2) adding 8-12 parts by weight of tertiary amino sultone and 3-5 parts by weight of tris(4-aminophenyl)amine to an N,N-dimethylformamide solvent, and then adding a 4-6% by weight sodium hydroxide solution thereto, heating to 70-90° C. for reaction, and after the reaction, removing the solvent by distillation under reduced pressure, washing and drying to obtain sodium sulfonate modified silane; (3) adding sodium sulfonate-modified silane and 2-amino-3-chloropropionic acid to N,N-dimethylformamide solvent, reacting at 75-85°C for 10-12 hours, and then rotary distilling, filtering and drying to obtain an intermediate; (4) Add 4,6-diamino-2-hydroxy-1,3,5-triazine and the intermediate to dimethyl sulfoxide, stir to dissolve and heat to 130-150°C, then dropwise add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, stir and reflux for 12-16 hours, cool, precipitate, filter and wash after the reaction to obtain quaternized sodium phenylsulfonate; The mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst in (1) is 1:1.2-1.4:0.02-0.03; The reaction time in (2) is 8-14h; The mass ratio of sodium sulfonate modified silane to 2-amino-3-chloropropionic acid in (3) is 1:2.1-3.4; The mass ratio of 4,6-diamino-2-hydroxy-1,3,5-triazine, intermediate, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 4-dimethylaminopyridine in (4) is 0.4-0.8:1:0.01-0.03:0.02-0.03; The preparation method of the silicon-modified phenolic resin is as follows: S1. Add 7-15 parts by weight of 4-chloromethylphenol and 6-10 parts by weight of sodium sulfonate modified silane to N,N-dimethylformamide solvent, stir to dissolve, react at 65-80 ° C for 5-8h, and then distill under reduced pressure, filter and dry to obtain quaternized phenol; S2. Dissolve 12-16 parts by weight of phenol in water, then add 1-2 parts by weight of cardanol, 0.6-1 parts by weight of quaternized phenol, 0.3-0.6 parts by weight of oxalic acid dihydrate and 8-13 parts by weight of polyformaldehyde, heat to 80-90°C and react for 2-4 hours to obtain silicon-modified phenolic resin.

2. A method for preparing a sewage treatment agent containing 1,4-butanediol as claimed in claim 1, characterized in that: The preparation method of the sewage treatment agent containing 1,4-butanediol is as follows: 1,4-butanediol, quaternized sodium phenyl sulfonate, silicon-modified phenolic resin and polyacrylamide are added into a stirrer, and stirred for 20-25 minutes, and then the sewage treatment agent containing 1,4-butanediol is obtained.